Anthraquinone-naphthacridone dyestuff



Patented Nov. 8, 1938 UNITED STATES PATENT OFFICE AN THRAQUINONE-NAPHTHACRID ONE DYE- STUFF Wilhelm Moser, Riehen,

ningen, Switzerland,

and Walter Fioroni, Binassignors t0 the firm of Society of ChemicalIndustry in Basle, Basel,

Switzerland No Drawing. Original 1937, Serial No. 119,88

application January 9, 8. Divided and this application January 3, 1938,Serial No. 183,228.

In Switzerland January 10, 1936 -1 Claim.

This invention relates to themanufacture of new dyestuffsof' theanthraquinone naphthacridone series by treating with a condensing agentan anthraquinone derivative which has at least 1 mol of the atomgrouping in which the one a: stands for hydrogen and the other x for aCOOR-group, OR being OH, 0- alkyl or 'halogen. The newanthraquinonenaphthacridones thusproduced contain at least once the atomgrouping and are valuable dyestuiis or intermediate products forobtaining dyestuffs. These dyestuffs represent therefore theN-azd-anthraquinonenaphthacridones. The new dyestuffs are distinguishedfrom the comparable naphthacridone dyestuffs by valuable properties,particularly by their levelling capacity. They'are dark powdersdissolving in sulfuric acid to orange, to brown, to olive and black-bluesolutions, yielding with hydrosulfite and caustic soda solution, brownto brown-red, violet-red and Bordeaux red vats, and dyeing the vegetablefiber Bordeaux red to violet, to green, to grey and brown tints.

The compounds which contain at least once the atom grouping ester; 1 mol1:5-diaminoanthraquin0ne and 2 mols 1-chloronaphthalene-2-carboxy1icacid ethyl ester; 1 mol l-amino-4-benzoylaminoanthra-' quinone and 1 mol1-chloronaphthalene-2-carboxylic ac-id ethyl ester; 1 moll-amino-S-benzoylaminoanthraquinone and 1 moll-chloronaphthalene-2-carboxylic acid ethyl ester; the condensationproduct from 1 mol 1:4-dichlor0- naphthalene and 2 molsl-chloroaminoanthraquinone-Z-carboxylic acid ethyl ester; thecondensation product from 1 mol 4:4'-diamin0-1:1'- dianthraquinonylamineand 2 mols l-chloronaphthalene-2-carboxylic acid.

As condensing agents capable of converting the above compounds intoacridone derivatives there come into question those Which are used forsimilar reactions provided that they do not simul taneously have asulfonating action. Such agents or processes are, for example, thetreatment with reducing agents in the presence of alkalies, for instancevatting (if :1: stands for a COOH-group or a COO-alkyl group); agentswhich convert the COOR-group into the CO-halogen group and then closethe ring; agents which withdraw water or the like. i

The new acridone derivatives which contain reactive groups may furtherbe condensed with certain compounds, for instance the new acridonederivative of the formula generally those which correspond to thegeneral formula ill in which one a: stands for a hydrogen atom and theother :0 stands for a NH-y group, wherein, 1 represents a radicalselected from the group of radicals consisting of aroyl radicals,anthraquinonyl radicals and the carbazolanthraquinonyl radicals derivingtherefrom, which products are dark powders, dissolving in sulfuric acidto orange, to brown, to olive and black-blue solutions, yielding withhydrosulfite and caustic soda solution brown to brown-red, violet-redand Bordeaux-red vats, and dyeing the vegetable fiber Bordeaux red toviolet, to green, to grey and brown tints.

The new acridone derivatives may be halogenated, nitrated andsubsequently reduced and if desired acylated, new dyestuifs beingobtained. Acridone derivatives may be produced which in addition to theacridone grouping here characterized contain other acridone groupings.

The following examples illustrate the invention, the parts being byweight; the ratio of parts by weight to parts by volume is that whichexists between the kilo and the litre:-

Example 1 part of 1-(onnaphthylamino-fii1-carboxylic acid ethyl ester)A-benzoylaminoanthraquinone ground wet are vatted in 600 parts of waterby means of 30 parts of sodium hydroxide solution of 30 per cent.strength and parts of sodium hydrosulfite for 1 hour at 65-70 C.; themass is filtered, the filtrate oxidized by blowing in air and againfiltered; the solid matter is washed neutral and dried. The dyestuifthus obtained is a 4- benzoylamino-l-a-naphthanthraquinone acridone ofthe formula It is a dark powder which dyes cotton very 1a.. and levelgreenish gray in a violet red vat, the sulfuric acid solution is orangeand when poured into water yields green-gray flocks. 7

Similar products are obtained when using the corresponding 4 (4 chloro)-benzoylaminoan thraquinone or 4 (3'methoxy) -benzoylaminoanthraquinonederivatives instead of the l-(al-lnaphthylamino-,c1-carboxylicacid-ethyl ester)- 4 benzoylaminoanthraquinone, or exchanging the aroylradicals of the benzene series for other acyl radicals, such as those ofthe phenoxy-acetic acid or of the furane carboxylic acid.

The 1 (on naphthylamino-fi1-carboxylic acid ethyl ester)-4-benzoylaminoanthraquinone may be made as follows:-

34.2 parts of 1-amino-4-benzoylaminoanthraquinone, 23.4 parts ofl-chloronaphthalene-2- carboxylic acid ethyl ester, 12 parts ofanhydrous sodium carbonate and 0.6 part of anhydrous cupric chloride aremixed together in 240 parts of nitrobenzene and the mixture is boiledfor hours under reflux. When the mixture is cooled it is filtered andthe solid matter is washed with a little nitrobenzene, then with tolueneand alcohol and finally with water and then treated with hydrochloricacid, washed neutral and dried.

The crystalline blue body thus obtained is a l-(ai-naphthylamino 61carboxylic acid ethyl ester) 4 benzoylaminoanthraquinone. It dissolvesto an olive brown solution in sulfuric acid; when this solution ispoured into water yellow brown flocks are produced.

The l-benzoylamino am naphthanthraquinoneacridone can also be producedby condensing the 1- (on-naphthylamino-[n-carboxylic acid)4-benzoylaminoanthraquinone as indicated in Example 1.

An isomeric 5-benzoylamino-u:a-naphthanthraquinoneacridone which dyesbrown tints from a violet vat can be obtained from l-amino-5-benzoylaminoanthraquinone.

Example 2 26 parts of 5-aminoanthraquinone-1:l:2:2- naphthacridone ofthe formula of the formula 0 i ll 00 \J dissolves in concentratedsulfuric acid to brownorange solutions. When precipitated in water thereare formed violet flocks. Cotton is dyed from a red vat brownish-violettints.

10 parts of this condensation product are introduced at 140 C. into amixture from parts of aluminium chloride and 20 parts of sodiumchloride, the whole is stirred for A hour at 0., taken up in water andhydrochloric acid,

heated to the boil, filtered hot and washed neutral while hot, and thendried.

The carbazol thus obtained of the formula it dissolves in concentratedsulfuric acid to redbrown solutions; when precipitated in water thereare formed brown flocks. Cotton is dyed from violet-brown vat fast browntints.

What we claim is:- The dyestuff of the formula 0 which product is a darkpowder, dissolving in sulfuric acid to a red-brown solution and in waterwith addition of hydrosulfite and caustic soda solution to aviolet-brown solution, and dyeing cotton from the vat fast level browntints.

WILHELM MOSER. WALTER FIORONI.

